EP0121269B1 - Verfahren zum Sterilisieren mittels Strahlung von Zusammensetzungen aus Polyolefinen - Google Patents

Verfahren zum Sterilisieren mittels Strahlung von Zusammensetzungen aus Polyolefinen Download PDF

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Publication number
EP0121269B1
EP0121269B1 EP84200098A EP84200098A EP0121269B1 EP 0121269 B1 EP0121269 B1 EP 0121269B1 EP 84200098 A EP84200098 A EP 84200098A EP 84200098 A EP84200098 A EP 84200098A EP 0121269 B1 EP0121269 B1 EP 0121269B1
Authority
EP
European Patent Office
Prior art keywords
irradiation
composition
compositions
process according
sterilization
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP84200098A
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English (en)
French (fr)
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EP0121269A1 (de
Inventor
Serge Blanc
Roger Van Asbroeck
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Solvay SA
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Solvay SA
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Publication date
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Priority to AT84200098T priority Critical patent/ATE35906T1/de
Publication of EP0121269A1 publication Critical patent/EP0121269A1/de
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Publication of EP0121269B1 publication Critical patent/EP0121269B1/de
Expired legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2/00—Disinfection or sterilisation of materials or objects, in general; Accessories therefor
    • A61L2/02—Disinfection or sterilisation of materials or objects, in general; Accessories therefor using physical processes
    • A61L2/08—Radiation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids

Definitions

  • the present invention relates to a process for the sterilization by irradiation of polyolefinic compositions. It relates more particularly to a process for the sterilization by gamma irradiation of compositions based on propylene polymers.
  • Polyolefins have also recently found an application in the manufacture of medical articles and food packaging generally subjected to sterilization treatments by gamma irradiation at doses usually between 0.5.10 4 and 6.10 4 Gy ( gray) (0.5 to 6 megarads).
  • the present invention provides a process for the sterilization by irradiation of polyolefinic compositions which does not cause the degradation phenomena mentioned above.
  • the invention relates for this purpose to a method for sterilization by irradiation, by a sterilizing dose of high energy radiation such as gamma rays, of polyolefin composition containing at least one phenolic antioxidant according to which the polyolefin composition contains an antioxidant which is the 2,2'-methylene-bis- (4-methyl-6-tert-butylphenol) terephthalate.
  • the polyolefin compositions to be sterilized according to the invention may also contain one or more other additives, generally chosen from the compounds defined below.
  • phenolic antioxidants such as alkylated monophenols.
  • alkylated monophenol mention may be made of 2,6-di-tert-butyl-p-cresol.
  • They may be other conventional secondary antioxidants, acting synergistically with phenolic antioxidants, such as thioesters, organic phosphites and mixtures thereof.
  • Thioesters which can be used are, on the one hand, the aliphatic esters of thiodipropionic acid and, on the other hand, the esters derived from aliphatic polyols and from alkylthiodipropionic acids.
  • aliphatic esters of thiodipropionic acid mention may be made of dilauryl-, distearyl- and dimyristyl-thiodipropionates.
  • esters derived from aliphatic polyols and from alkylthiodipropionic acids include octamethylene-bis (3-dodecylthiopropionate), bis (ethylene-3-octadecylthiopropionate) sulfide and tetrakis (3-thiododecylpropionate) ) of pentaerythritol.
  • Organic phosphites which can be used are, on the one hand, trialkyl- and trialkylarylphosphites and, on the other hand, cyclic diphosphites derived from pentaerythritol.
  • trialkyl- and trialkylarylphosphites mention may be made of trinonyl-, tri (nonylphenyl) - and tri (2,4-di-tert-butyl-5-methyl) phenylphosphites.
  • cyclic diphosphites derived from pentaerythritol mention may be made of distearylpentaerythritol diphosphite.
  • the aliphatic esters of thiodipropionic acid, the cyclic diphosphites derived from pentaerythritol and their mixtures are preferred and, among them, very particularly the mixtures of diphosphite of distearlpentaerythritol and of dilaurylthiodipropionate.
  • the polyolefin compositions to be sterilized according to the invention may also contain a stabilizing compound which is a calcium salt of a saturated aliphatic monocarboxylic acid.
  • a stabilizing compound which is a calcium salt of a saturated aliphatic monocarboxylic acid.
  • a stabilizing compound which is a calcium salt of a saturated aliphatic monocarboxylic acid.
  • such salts mention may be made of stearate, palmitate and 2-ethylhexanoate.
  • the preferred salt is calcium stearate.
  • the antioxidant or the mixture of antioxidants as well as the possible stabilizing compound are used at the usual stabilizing doses. These doses are usually comprised, for each of the additives, between 0.001 and 10% by weight of the alpha-olefin polymers entering into the compositions, preferably between 0.005 and 5% by weight and more particularly between 0.01 and 0.5 % in weight.
  • the sterilized compositions according to the invention may contain other usual additives such as, for example, other antioxidants such as tetrakisphenols, amines, reinforcing agents, pigments, lubricants, fillers, antistatic agents, etc.
  • other antioxidants such as tetrakisphenols, amines, reinforcing agents, pigments, lubricants, fillers, antistatic agents, etc.
  • the alpha-olefin polymers entering into the compositions to be sterilized according to the invention are polymers containing at least 50 mol% and preferably at least 75 mol% of terminal unsaturated olefins the molecule of which contains from 2 to 18 and of preferably from 2 to 6 carbon atoms such as ethylene, propylene, butene-1, pentene-1, methylbutenes-1, hexene-1 and 3- and 4-methylpentenes-1. They are more particularly polymers containing tertiary carbon atoms such as highly isotactic crystalline polymers of butene-1, 4-methylpentene-1, and very particularly, propylene.
  • They may also be copolymers of these alpha-olefins with one another and / or with diolefins comprising from 4 to 18 carbon atoms, such as non-conjugated aliphatic diolefins such as, for example, 1,4-hexadiene or such that alicyclic diolefins having an endocyclic bridge such as dicyclopentadiene for example.
  • these may be block copolymers which consist of successions of chain segments of variable length, each segment consisting of a homopolymer of an alpha-olefin or of a random copolymer comprising an alpha-olefin and at least one comonomer chosen from alpha-olefins and diolefins.
  • the polyolefin compositions to be sterilized according to the invention can also be based on mixtures of two or more polymers as described above, as well as other polymers compatible with the latter.
  • the polymers which can be used can be prepared according to known methods of polymerization of alpha-olefins at low pressure.
  • highly isotactic crystalline homopolymers of propylene can be prepared in the presence of stereospecific catalytic systems based on organometallic compounds and titanium chlorides being at a valence lower than its maximum valence.
  • the additives can be incorporated into the polymer in any manner known per se, for example by impregnating the polymer in powder or granules by means of a solution of the antioxidants, or alternatively by mixing a solution or a suspension of the polymer with a solution of the antioxidants .
  • the incorporation can be carried out, for example, either in a mixer or a mill where the solvent is evaporated, or by mixing on heated cylinders or by extrusion of a mixture of the polymer and the stabilizing composition.
  • the polyolefin compositions are sterilized by irradiation.
  • This sterilization is most conveniently carried out after transformation of the compositions into shaped articles.
  • the high energy radiation usable for sterilization can be gamma rays supplied by a source of cobalt 60, for example. Irradiation with other radiation, such as X-rays or high energy electrons, can also be carried out, provided that it ensures effective sterilization of the compositions.
  • the sterilizing irradiation dose is between 0.5.10 4 and 6.10 4 Gy, preferably between 2.10 4 and 5.10 4 Gy.
  • the intensity of the irradiation is generally such that it corresponds to an absorbed dose of between 2,500 and 20,000 Gy / hour.
  • the invention also relates to the sterilization of articles shaped from the polyolefin compositions defined above.
  • These compositions are suitable for use by all the conventional processes for transforming plastics into shaped articles, and more particularly by injection and by extrusion.
  • Examples of sterilizable shaped articles according to the invention which can be obtained from said polyolefin compositions are medical articles such as syringes, forceps, baxters, surgical forceps, etc. and packaging items such as bags, sachets, etc.
  • a stabilized polyolefin composition is prepared by dry mixing of the following constituents: 100 parts by weight of a crystalline polymer of propylene with a melting index (MFI) measured at 230 ° C. under a load of 2.16 kg (ASTM standard) D 1238) of 12 g / 10 min;
  • This stabilized composition (1) is transformed by injection molding into 2 mm thick plates then subjected to sterilization by irradiation by means of a dose of 2 megarad (2.10 4 Gy) of gamma rays supplied by a source of cobalt. 60.
  • the irradiated and non-irradiated platelets are subjected to colorimetric measurements in a colorimeter of the HUNTERLAB type.
  • the same colorimetric measurements are applied to injected and irradiated platelets in the same manner as the platelets according to the invention, from polyolefin compositions identical to that described above but in which the terephthalate has been replaced.
  • the colorimetric coordinate b which, in the colorimetric system L, a, b of Hunter, represents the chromaticity along the yellow axis, is collected for each sample, before and after irradiation. blue, an increase in the value of this coordinate (+ ⁇ b) indicating yellowing (ASTM-D2244-79 standard).

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Apparatus For Disinfection Or Sterilisation (AREA)
  • Artificial Filaments (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)

Claims (5)

1. Verfahren zum Sterilisieren mittels Strahlung durch eine sterilisierende Dosis hochenergetischer Strahlen wie gamma-Strahlen, von Polyolefinzusammensetzungen, die mindestens ein phenolisches Antioxydans enthalten, dadurch gekennzeichnet, daß die polyolefinische Zusammensetzung 2,2'-Methylen-bis-(4-methyl-6-tert-butylphenol)-terephtalat enthält.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Zusammensetzung außerdem ein sekundäres Antioxydans enthält, ausgewählt unter den Thioestern, den organischen Phosphiten und deren Mischungen.
3. Verfahren nach Anspruch 2, dadurch gekennzeichnet, daß das sekundäre Antioxydans eine Mischung von Dilaurylthiodipropionat und Distearylpentaerythritoldiphosphit ist.
4. Verfahren nach einem der vorgehenden Ansprüche, dadurch gekennzeichnet, daß die Zusammensetzung außerdem ein Kalziumsalz einer gesättigten aliphatischen Monocarbonsäure enthält.
5. Verfahren nach einem der vorgehenden Ansprüche, dadurch gekennzeichnet, daß das alpha-Olefinpolymer, welches in die Zusammensetzung eingeht, ein kristallines Propylenpolymer ist.
EP84200098A 1983-02-07 1984-01-26 Verfahren zum Sterilisieren mittels Strahlung von Zusammensetzungen aus Polyolefinen Expired EP0121269B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT84200098T ATE35906T1 (de) 1983-02-07 1984-01-26 Verfahren zum sterilisieren mittels strahlung von zusammensetzungen aus polyolefinen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8302005A FR2540504B1 (fr) 1983-02-07 1983-02-07 Procede pour la sterilisation par irradiation de compositions polyolefiniques, compositions polyolefiniques ainsi sterilisees et articles faconnes a partir de ces compositions
FR8302005 1983-02-07

Publications (2)

Publication Number Publication Date
EP0121269A1 EP0121269A1 (de) 1984-10-10
EP0121269B1 true EP0121269B1 (de) 1988-07-27

Family

ID=9285733

Family Applications (1)

Application Number Title Priority Date Filing Date
EP84200098A Expired EP0121269B1 (de) 1983-02-07 1984-01-26 Verfahren zum Sterilisieren mittels Strahlung von Zusammensetzungen aus Polyolefinen

Country Status (8)

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EP (1) EP0121269B1 (de)
AT (1) ATE35906T1 (de)
CA (1) CA1235281A (de)
DE (1) DE3472895D1 (de)
ES (1) ES8500304A1 (de)
FR (1) FR2540504B1 (de)
IE (1) IE56442B1 (de)
NO (1) NO157084C (de)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0091152A1 (de) * 1982-04-05 1983-10-12 SOLVAY & Cie (Société Anonyme) Stabilisierte Zusammensetzungen von alpha-Olefinpolymeren

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1050802A (de) *
US3248248A (en) * 1962-04-20 1966-04-26 Monsanto Co Light stable polymer composition
FR1485977A (fr) * 1966-07-04 1967-06-23 Eastman Kodak Co Compositions thermoplastiques stables à la lumière
JPS4939637A (de) * 1972-08-24 1974-04-13
GB1480435A (en) * 1974-02-11 1977-07-20 Exxon Research Engineering Co Bisphenol derivatives and uses thereof
FR2264002B1 (de) * 1974-03-12 1977-09-23 Organo Synthese Ste Fse

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0091152A1 (de) * 1982-04-05 1983-10-12 SOLVAY & Cie (Société Anonyme) Stabilisierte Zusammensetzungen von alpha-Olefinpolymeren

Also Published As

Publication number Publication date
DE3472895D1 (en) 1988-09-01
FR2540504A1 (fr) 1984-08-10
ES529476A0 (es) 1984-10-01
EP0121269A1 (de) 1984-10-10
ES8500304A1 (es) 1984-10-01
CA1235281A (fr) 1988-04-19
IE840270L (en) 1984-08-07
NO840436L (no) 1984-08-08
NO157084C (no) 1988-01-20
FR2540504B1 (fr) 1986-03-07
ATE35906T1 (de) 1988-08-15
NO157084B (no) 1987-10-12
IE56442B1 (en) 1991-07-31

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